WO1999057215A1 - Water-activatable polymers for ink jet-imprintable constructions - Google Patents
Water-activatable polymers for ink jet-imprintable constructions Download PDFInfo
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- WO1999057215A1 WO1999057215A1 PCT/US1999/009682 US9909682W WO9957215A1 WO 1999057215 A1 WO1999057215 A1 WO 1999057215A1 US 9909682 W US9909682 W US 9909682W WO 9957215 A1 WO9957215 A1 WO 9957215A1
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- water
- activatable
- acrylic
- tacky
- weight
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/006—Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/0256—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet the transferable ink pattern being obtained by means of a computer driven printer, e.g. an ink jet or laser printer, or by electrographic means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1733—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1733—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
- B44C1/1737—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff on a substrate unsuitable for direct deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/175—Transfer using solvent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/175—Transfer using solvent
- B44C1/1752—Decalcomanias provided with a particular decorative layer, e.g. being specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/504—Backcoats
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0036—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers dried without curing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Definitions
- This invention relates to water-activatable polymers that are ink jet imprintable and can be used for adhesive image transfer, and constructions made with such polymers.
- Labels, tapes and similar constructions are ubiquitous in modern society. Many such constructions include a release liner coated with adhesive, such as a pressure-sensitive adhesive (PSA), which is laminated to a paper or film face stock. Removal of the release liner allows the construction ⁇ face stock coated with adhesive ⁇ to be adhered to a substrate.
- PSA pressure-sensitive adhesive
- PSAs typically are not hydrophilic, making it difficult to print on them directly with water-based ink jet printer inks. Instead, only the face stock or liner is ink-receptive. The unsuitability of such PSAs for use in ink jet printers is compounded by the tendency of the adhesives to block the printer ports in the printers.
- European Patents Nos. 199,468 and 297,451 describe a method for compounding water-activatable hot melt adhesives comprising polyaklylenimine or other vinyl heterocyclicmonomers, a hydroxy-substituted organic compound, a plastizier, tackifier, and filler, and an antioxidant. No mention is made of making water-activatable emulsion acrylic adhesives.
- water-receptive, water-dispersible, acrylic polymers that are non-tacky when dry but become tacky when wet, and which are particularly useful as water-activatable adhesives for image transfer constructions.
- the composition comprises an acrylic-based polymer prepared by emulsion polymerization of a monomer mixture comprising, based on the total weight of monomers, from about 40 to 70% by weight of one or more alkyl acrylates, the alkyl group of which has from 4 to about 8 carbon atoms; from about 5 to 15% by weight of methyl acrylate; from about 7 to about 17% by weight of vinyl acetate; and from about 10 to 25%) by weight of methacrylic acid and/or acrylic acid.
- a monomer mixture comprising, based on the total weight of monomers, from about 40 to 70% by weight of one or more alkyl acrylates, the alkyl group of which has from 4 to about 8 carbon atoms; from about 5 to 15% by weight of methyl acrylate; from about 7 to about 17% by weight of vinyl acetate; and from about 10 to 25%) by weight of methacrylic acid and/or acrylic acid.
- the polymers can be cast as continuous films that, when dry, are non-tacky to the touch at room temperature, but when exposed to moisture, such as the water in an ink jet printer ink, become tacky.
- Films cast from the emulsion polymers are water-receptive or hydrophilic, repulpable, water-activatable and transparent to visible light. They can be directly printed upon using a water-based ink and, after activation and adhesion to a substrate, can be removed from a substrate by application of water.
- an ink jet-imprintable, water-activatable adhesive construction is provided.
- the construction comprises at least one layer of water-activatable acrylic polymers, coated on at least one water-impermeable layer, such as a layer of UV varnish, which is applied to a coated or uncoated flexible backing (i.e., a release liner).
- a continuous, water-soluble, protective detack layer is coated on the water-activatable acrylic polymer layer(s).
- the water-activatable layer is non-tacky when dry, but becomes tacky when exposed to water. Consequently, when printed with a water-based ink jet printer ink, the detack layer dissolves within the region of the printed image, and the polymer layer(s) become tacky within the region of the printed image, but not in other regions that were not directly printed on.
- the construction is useful as a label or decorative image sheet, and is applied to an object or surface by adhering the water-activated polymer (which is now tacky) to the object and, removing some or all of the flexible substrate or liner.
- FIG. 1 is a schematic, cross-sectional illustration of one embodiment of an ink jet-imprintable, water-activatable construction prepared in accordance with the present invention.
- the present invention provides acrylic polymers that are non-tacky when dry, yet hydrophilic, water-dispersible, and water-activatable ⁇ even by a small amount of moisture, such as the water in the ink of a personal ink jet printer ⁇ and become tacky and functional as a pressure-sensitive adhesive.
- the activated adhesives adhere to the substrate yet are removable by further application of water.
- the adhesives are receptive to the inks used in ink jet printers, including colored inks, and are transparent to visible light.
- the adhesives may also be receptive to inks containing metal flakes or pigments.
- the acrylic polymers are prepared by emulsion polymerization of a monomer mixture comprising, on a percent by weight basis, based on the total weight of monomers (a) from about 40 to 70% of at least one alkyl acrylate having an alkyl group containing 4 to about 8 carbon atoms, with a mixture of two such alkyl acrylates being preferred; (b) from about 5 to 15%) of methyl acrylate; (c) from about 5 to 20%) of vinyl acetate; and (d) from about 5 to 25% of one or more of methacrylic acid and acrylic acid, with a mixture of the two — e.g., from about 1 to 5% methacrylic acid and from about 5 to 20%> acrylic acid ⁇ being more preferred.
- a monomer mixture comprising, on a percent by weight basis, based on the total weight of monomers (a) from about 40 to 70% of at least one alkyl acrylate having an alkyl group containing 4 to about 8 carbon atoms, with a mixture of two
- the monomer mixture contains no methyl methacrylate.
- the monomer mixture can include up to about 5% by weight, more preferably less than about 3.5%> by weight, of methyl methacrylate, based on the total weight of monomers.
- a mixture of alkyl acrylates as the first monomeric component.
- Useful alkyl acrylates include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and the like. A mixture of 2-ethylhexyl acrylate and butyl acrylate is preferred.
- the acid monomers impart polarity and hydrophihcity to the resulting polymers.
- the identity and relative amounts of monomers used to form the polymers are selected so that the polymers have a sufficiently high glass transition temperature (T g ) and/or other properties (e.g., high plateau modulus) such that the polymers are non-tacky to the touch at room temperature, when dry. To that end, it is preferred to use a substantial amount of vinyl acetate and/or the acid monomers .
- T g glass transition temperature
- other properties e.g., high plateau modulus
- non-tacky to the touch means that the copolymers, when cast as a film and dried, do not feel sticky, under conditions of room temperature (about 20-25 °C) and normal relative humidity (less than about 25% RH). The copolymers appear to remain non-
- the monomer mixture comprises, on a percent-by-weight basis, based on the total weight of monomers, from about 10 to 20% butyl acrylate; from about 40 to 60%) 2-ethylhexy acrylate; from about 5 to 15% methyl acrylate; from about 10 to 20% vinyl acetate; from about 5 to 20% acrylic acid; and from about 1 to 5% methacrylic acid.
- the monomer amounts are, approximately, 12%o butyl acrylate, 48%o 2-ethylhexyl acrylate; 9% methyl acrylate; 12% vinyl acetate; 16%) acrylic acid; and 3% methacrylic acid.
- the water-activatable acrylic copolymers are prepared by free-radical emulsion polymerization, preferably in an oxygen-free environment, in the presence of suitable polymerization initiators and emulsifiers (surfactants). Enough surfactant is included to form a stable emulsion without causing phase separation.
- suitable polymerization initiators and emulsifiers surfactants.
- One or more activators, redox agents and chain transfer agents also are preferably employed in the preparation of the polymers.
- nonionic, anionic, and/or cationic surfactants can be used to prepare the acrylic copolymers, it is preferred to employ a mixture of two or more surfactants, for example, Disponil FES77, a sodium lauryl ether surfactant, available from Henkel of America, Inc. (King of Prussia, PA); TSPP (sodium pyrophosphate), available from J.T. Baker (Mallinckrodt Baker, Inc., Phillipsburg, NJ); and Aerosol OT-75, a sodium dioctyl sulfusccinate surfactant, available from American Cyanamid (Wayne, NJ).
- Disponil FES77 a sodium lauryl ether surfactant
- TSPP sodium pyrophosphate
- J.T. Baker Mallinckrodt Baker, Inc., Phillipsburg, NJ
- Aerosol OT-75 a sodium dioctyl sulfusccinate surfactant, available from American Cyanamid (Wayne, NJ
- surfactants include cetyl trimethyl ammonium bromide, available from Aldrich (Milwaukee, WI); AR-150, a nonionic, ethoxylated rosin acid emulsifier available from Hercules, Inc.
- Nonlimiting examples of useful polymerization initiators include water-soluble initiators, for example, persulfates, such as sodium persulfate (Na j S j Og) and potassium persulfate; peroxides, such as hydrogen peroxide and tert-butyl hydroperoxide (t-BHP); and azo compounds,
- VAZOTM initiators such as VAZOTM initiators; used alone or in combination with one or more reducing agents or activators, for example, bisulfites, metabisulfites, ascorbic acid, erythorbic acid, sodium formaldehyde sulfoxylate (available from Henkel of America, Inc.), ferrous sulfate, ferrous ammonium sulfate, and ferric ethylenediarninetetraacetic acid. Enough initiator is used to promote free-radical polymerization of the monomers.
- reducing agents or activators for example, bisulfites, metabisulfites, ascorbic acid, erythorbic acid, sodium formaldehyde sulfoxylate (available from Henkel of America, Inc.), ferrous sulfate, ferrous ammonium sulfate, and ferric ethylenediarninetetraacetic acid.
- Enough initiator is used to promote free-radical polymerization of the monomers.
- n-DDM n-dodecyl mercaptan
- t-DDM t-dodecyl mercaptan
- monothioglycerol mercapto acetates
- long chain alcohols e.g., from about 0.01 to 0.5%> by weight of the monomers
- the emulsion polymers are prepared with excellent conversions at a reaction temperature of around 70 °C, in the presence of from about 0.5 to about 1% by weight, based on the weight of the monomers, of a persulfate or equivalent catalyst, with the monomer mixture being fed over a period of about 3 hours.
- Reaction pH can be adjusted by addition of sodium bicarbonate or a similar agent, to within a range of from about 4.0 to about 6.0.
- the emulsion polymers are prepared by first mixing one or more pre-emulsions containing conventional surfactants, sodium bicarbonate, and some or all of the monomers in deionized water; adding reactive surfactants and other reactor ingredients (e.g., Fe-EDTA, AR 150, hydrogen peroxide) to a reactor under nitrogen; heating the reactor to 70 ° C ⁇ 2 ° C and then adding a pre-emulsion charge, overtime (preferably in stepped or mixed feed sequences); adding an initiator charge containing, for example, potassium persulfate; continuing the pre-emulsion feeds and addition of any accelerators; adding any post-reaction charges (e.g., t-BHP, ascorbic acid, and more water); cooling the reactor contents to below 35 ° C; and filtering the emulsion polymer. Before filtering the reaction mixture, a biocide, for example, Kathon LX (available as a
- the copolymers are prepared by sequential polymerization and the monomers are allowed to react in distinct stages.
- separate pre-emulsions of monomers, surfactants, initiators and other components are prepared, a reactor is charged with an initial soap (surfactant) solution and catalyst (initiator) solution, a first pre-emulsion of monomers is gradually fed into the reactor, and polymerization is initiated and allowed to propagate.
- a second pre-emulsion of monomers is gradually fed into the reactor and polymerization continues.
- the result is a copolymer system of emulsified copolymer particles quite distinct from emulsion copolymers prepared by batch polymerization.
- Water-activatable, emulsion acrylic copolymers were prepared by sequential polymerization using the polymerization protocol described below.
- the monomer mixture consisted of 12% BA, 48% 2-EHA, 9% MA, 12% VAc, 16% AA, and 3% MAA, based on the total weight of monomers.
- Table 1 summarizes the identities and amounts of monomers, surfactants, initiators, and other components used to prepare the acrylic copolymers of Examples 1-3.
- a jacketed, multi-neck reaction vessel equipped with nitrogen inlet valve, stirrer and thermometer was charged with initial reactor charge A, and the temperature was raised to 70 °C.
- soap solution B and monomer charges Cl and C2 were prepared.
- Pre-emulsions I and II were prepared by mixing one-half of soap solution B with monomer charge Cl and one-half with monomer charge C2. When the reactor temperature reached 70°C,
- the resulting emulsion acrylic copolymers had a pH of from about 4.0 to 6.0; a solids content of about 50%>, as determined by gravimetric analysis; a viscosity of about 12,500 cps, as determined with a Brookfield viscometer, RV (#4@12 rpm); T g of about -17°C, as determined by differential scanning calorimetry (DSC); a gel content of about 16%; a number average molecular weight (M N ) of from about 12,690 to 14,116; and a weight average molecular weight (M w ) of from about 58,000 to 73,000, both M N and M w being determined by gel permeation chromatography.
- Example 2 Example 2
- Water-activatable emulsion acrylic copolymers were prepared as in Example 1, but without using sequential polymerization. Instead, a single monomer charge C was pre-emulsified and fed into the reactor over a 180-minute period.
- the copolymers had a pH of about 4.0 to 6.0; a 50% solids content; a viscosity of about 5,900 cps; T g of about -17°C; a gel content of about 28%; M N of from about 12,400 to 13,400; and M w of from about 77,000 to 86,000.
- Example 3 Example 3
- Acrylic copolymers were prepared using the sequential polymerization reaction protocol of Example 1, but the monomer charges also included methyl methacrylate. Monomer weight percentages were 12% BA, 46% 2-EHA, 8% MA, 12% VAc, 15% AA, 3% MAA, and 5% MMA. The resulting copolymers had a pH of about 4.0 to 6.0; a 52% solids content; a viscosity of about 20,000 cps; and a T g of about -15°C. The copolymers of Example 3 exhibited poor image transfer properties, as compared to the transfer properties of Examples 1 and 2.
- Reaction Component Charge Charge 1+2 1+2, Charge l,dry Charge 1 Charge 2 1+2 1+2, dry 2 dry 1 basis basis basis
- Di- water 180 180 0 180 0 180 180 0
- the dried sample was then wiped with a damp paper towel, thereby activating the adhesive, and laminated to a paper face stock (50 lb/ream DSXTM paper, a bright white, uncoated paper designed for high speed converting, from Avery Dennison's Fasson Roll Division, Painesville, OH), and the release liner was removed.
- the exposed acrylic copolymer face was then wiped with a damp paper towel, thereby activating the adhesive, and then adhered to a glass or stainless steel panel, and standard shear, 90° peel, and 180° peel tests were performed.
- shear was determined in accordance with Pressure-Sensitive Tape Council (PSTC) test method #7 (6th Ed.) The overlap dimensions were 1/2 in. x 1/2 in., with a static load of 500g. The test was conducted at room temperature at a 20 ft/min. draw rate.
- PSTC Pressure-Sensitive Tape Council
- the image transfer sheet 10 comprises 4 primary elements: a flexible backing 20, a water-impermeable layer or layers 40, a hydrophilic, ink-receptive, water-activatable adhesive 60, and a protective, water-soluble detach layer 80.
- the flexible backing preferably comprises a paper sheet 20, having an outer surface 22 and an inner surface 24.
- a very thin layer of low-density polyethylene (LDPE) 26 is coated on the inner surface 24 of the paper sheet.
- LDPE-coated paper is 92 lb. per ream coated paper sold as 9 LDMT-70 bleached/13 LDTL, available from Jen-Coat, Inc. (Wesleyan, MA).
- -9- Coated atop the LDPE-coated paper is a first layer 40a of water-insoluble UV varnish.
- the varnish can be applied as a liquid and then cured with ultraviolet (UV) light.
- the varnish is applied at a coat weight (measured after drying) of from about l-5g/m 2 , more preferably, about 2.5 to 4.5, g/m 2 .
- a thin layer (approximately 0.5g/m 2 ) of silicone is used in place of the UV varnish layer 40a.
- a second UV varnish layer 40b also insoluble in water, is coated on the first UV varnish layer. Because the layers 40a and 40b are applied in separate coating steps, they are separable from one another across their interface 42.
- the second layer of UV varnish is applied to the dried, first layer of UV varnish at a coating of about 4 to 6 g/m 2 .
- Nonlimiting examples of UV varnishes include Envirocure UV-1801, available from
- a thin (approximately 0.5 g/m 2 ) layer of silicone can be used as an alternative to the first UV varnish layer.
- Other UV varnish alternatives include water-based, solvent-based, and hot melt varnishes.
- This first layer of acrylic polymers is water-activatable, becoming tacky when wet. It is preferably applied using a Meyer rod.
- a much thinner layer of water-receptive, water-activatable acrylic copolymers 60b is applied directly to the first layer of acrylic copolymers 60a, using a flexo-gravure coating technique, at a coat weight of from about 2 to 5 g/m 2 .
- a water-soluble, protective detach layer 80 is coated on the outer surface of the second layer of acrylic copolymers 60b.
- the detach layer preferably is comprised of polyacrylic acid (PA A), polyvinyl alcohol (PVOH) and a water-soluble starch, and is applied as a water-based coating (approximately 8 to 9% solids), which is then dried to a coat weight of from about 1 to 2g/m 2 .
- a preferred detach layer is applied as a coating comprising 3% PAA, 2% PVOH, 3.5% starch and 91.5% water, on a percent-by- weight basis. More generally, suitable detach layers can be prepared using between about 1 to 8% PAA, 1 to 5% PVOH, and 2 to 10% starch.
- a biocide such as Kathon LX, available as a 1.5% solution from Rohm & Haas (Philadelphia, PA) is added to enhance shelf life.
- the detack layer improves product handling and storage, enhances sheet feeding through desktop printers, and generally protects
- the detack layer also facilitates a clean break between the printed image and the non-imaged regions of the image transfer sheet.
- the starch promotes a clean break by rendering the detack layer somewhat brittle.
- films made entirely of PVOH are less brittle and would tend to transfer un-imaged regions along with the imaged regions of the sheet.
- the starch also helps balance the very hydroscopic PAA. A detack layer formed entirely of PAA, when exposed to a humid environment, would likely become tacky to the touch as it absorbed ambient moisture from the air.
- the non-aqueous components of the detack layer ⁇ PAA, PVOH, and starch - are available from a variety of vendors, well-known to those skilled in the art of adhesive and printable construction formulations.
- a presently preferred PVOH is Airvol 107, a water-soluble polymer made by alcoholysis of polyvinyl acetate, available from Air Products & Chemicals, Inc. (Allentown, PA). Airvol 107 combines high tensile strength with ease of film formation.
- a presently preferred starch is Cerestar 12640 Polar Tex-Instant Starch, a pre-gelatanized, stabilized and crosslinked, waxy maize starch (hydroxypropyl distarch phosphate), having a minimum particle size of 90, available from Cerestar USA, Inc. (Hammond, IN).
- the detack layer can be reformulated depending on the application envisioned for the image transfer sheet. For example, where the image transfer sheet is to be used to transfer water-removable "tatoos" to the skin, the detack layer is formulated in one embodiment with 84.5% water, 2.0% Airvol 107 starch, 10% water-activatable adhesive, and 1.5% Kathon LX biocide.
- the adhesive (described above) imparts additional tack when wet to promote adhesion to the skin.
- image transfer sheets can be prepared as thin sheets or rolls, such as sheets of labels where, for example, the water-activatable polymer layer has a thickness of from between 0.5 and 2 mils and the flexible backing has a similar small dimensional thickness. More preferably, the two layers of water-activatable copolymers have a combined thickness that is sufficiently great as to minimize dot gain ⁇ lateral movement of a dot of ink imprinted on the image transfer sheet.
- the image transfer sheets with water-absorbent materials (i.e., the water-activatable copolymer layers plus the detack layer) having a combined thickness of about one mil (about 0.025 mm).
- water-absorbent materials i.e., the water-activatable copolymer layers plus the detack layer
- the image transfer sheet 10 is non-tacky when dry, at room temperature and normal relative humidity (less than about 25% RH).
- the detack layer 80 is water-soluble, and the water-activatable copolymer layers 60a and 60b are water-receptive and become tacky when exposed to even a small amount of moisture, such as the water in a water-based ink jet ink. Consequently, when the image transfer sheet is passed through an Inkjet printer and imprinted with an image, tacky regions form in the upper layers 60a, 60b and 80 of the sheet.
- -11- are thin and water-receptive, and they become activated across their entire cross-sectional thickness, from the outer surface of the detack layer 80 to the interface between the first hydrophilic, water-activatable polymer 60a and the second UV varnish layer 40b.
- the sheet becomes tacky all the way through to the second UV varnish layer, which is water-resistant.
- the printed image can be transferred directly to an object by applying the now tacky top surface of the sheet to the object, using manual pressure, and peeling away the unactivated regions of the sheet along with the first UV varnish film layer and the flexible backing.
- a clean break forms between the imaged (tacky) and non-imaged (non-tacky) regions of the construction. The clean break is facilitated by the brittle detack layer 80 (made brittle by the starch) and the brittle second (inner) UV varnish layer 40. What remains is a crisp, transferred image, protected on its outer surface by the second UV varnish film layer.
- Examples 1-3 Printing tests conducted with Examples 1-3 reveal that the water-activatable acrylic copolymers of Examples 1 and 2 can be used to form image transfer sheets that provides good image transfer ⁇ generally exceeding 80%, and even achieving 100% image transfer ⁇ after being run through an ink jet printer and applied to a substrate. Similar constructions prepared using example 3, however, provided less satisfactory results, with only partial image transfer.
- Example 2 of the present invention Using a water-activatable composition prepared in accordance with Example 2 of the present invention, image transfer sheets were constructed in the above-described manner, printed with a solid image in an ink jet printer, and applied to 24 different substrates so that the quality of the transferred images could be evaluated.
- the water-activatable copolymers were applied at a coat weight of about 24 to 30 g/m 2 (dry weight). After applying an imaged sheet to a substrate at room temperature, using manual pressure, the imaged sheet was allowed to dwell on the substrate for about one to three minutes before peeling back the release liner and the non-imaged areas of the sheet. This allowed any excess moisture in the sheet to permeate the porous substrates.
- compositions of the present invention facilitated good image transfer to all but four of the test substrates, at room temperature.
- the terms “good, “fair” and “poor” are used to describe image transfer from the imprinted transfer sheet to the substrate.
- good means the image transferred cleanly (more or less completely) to the substrate;
- fair means the transferred image has a broken border, but otherwise the image transferred well; and
- poor means the transferred image is broken, with only partial transfer.
- constructions made with the water-activatable acrylic copolymers formulated according to Example 2 provided good image transfer, and essentially 100% of the imprinted image was transferred from the image transfer sheet to the substrate. In contrast, it is thought that the best commercially available image transfer sheets provide only 60% to 80% image transfer. Waxy
- Image transfer was improved when the release liner was peeled off in a fast, fluid motion, as opposed to a slow peel-off.
- the un-imaged portions of the transfer sheet break away cleanly from the imaged regions, which are left behind on the substrate and are crisp and distinct.
- a small portion of the un-imaged transfer sheet may not completely detach from the trailing edge of the imaged region but, instead, may be left behind on the substrate. If this occurs, the small amount of non-imaged, residual transfer sheet material can be removed without affecting the transferred image by pressing a piece of tape over the residue and lifting the residue from the substrate.
- the image transfer sheets of the present invention were readily imprinted in all three ink jet printers. Images transferred from the sheets were characterized by high color densities, higher even than the densities on plain photocopy paper, for most colors.
- a transferred image that has been applied to a substrate can be removed from the substrate by, e.g., swiping the image with a damp cloth.
- the UV varnish film protecting the image can be removed with an ordinary household cleaner.
- more permanent images are desired and can be formed by, e.g., incorporating one or more crosslinking components or layers into the construction.
- a crosslinking promoter layer can be coated on top of one or more layers of the water-activatable polymers.
- Crosslinking could then be promoted by activation with the water in an ink jet ink, with the water carrying the crosslinking agents down into the water-activatable copolymer layer(s) as it migrates into the construction.
- crosslinking promoters include zinc, aluminum, and zirconium salts, such as zinc acetate, zinc octoate, aluminum acetylacetonate, and zirconyl ammonium carbonate. 0.2 to about 2% by weight of such crosslinkers can be coated on the uppermost layer of water-activatable polymers to form a percolating crosslinker layer.
- an epoxy-functionalized monomer such as glycidyl methacrylate (GMA)
- GMA glycidyl methacrylate
- Heat-activated crosslinking should result in a water-permanent, three
- a UV-curable adhesive can be employed as a second adhesive.
- a UV-curable PSA can be substituted for one of the water-activatable layers, adjacent to the UV varnish. Once cured, the UV-curable PSA layer should improve the water-fastness or permanence of the transferred image.
- Nonlimiting examples of UV-curable PSAs are found in U.S. patent no. 5,686,504 (Ang), incorporated by reference herein.
- Other suitable UV-curable adhesives are available from National Starch and Chemical Co. (Bridgewater, NJ), Reichhold Chemicals, Inc. (Research Triangle Park, NC) and H.B. Fuller Co.
- the acrylic copolymers become activated (tacky) when exposed to water or solvent, and the tacky region(s) of an imaged sheet becomes transferable to a substrate.
- the adhesives and constructions described herein are intended to be used in a variety of applications, with all manner of graphic, as well as textual, images.Thus, a child can draw on an image transfer sheet with a water-based ink, thereby activating the imaged regions of the sheet, and then transfer the drawing to a substrate using manual pressure.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99922777A EP1086187A1 (en) | 1998-05-01 | 1999-05-03 | Water-activatable polymers for ink jet-imprintable constructions |
BR9911780-0A BR9911780A (en) | 1998-05-01 | 1999-05-03 | Water-activated polymers for buildings that can be printed with inkjet |
JP2000547174A JP2002513701A (en) | 1998-05-01 | 1999-05-03 | Water-activated polymer for inkjet printable structures |
MXPA00010728A MXPA00010728A (en) | 1998-05-01 | 1999-05-03 | Water-activatable polymers for ink jet-imprintable constructions. |
CA002329838A CA2329838A1 (en) | 1998-05-01 | 1999-05-03 | Water-activatable polymers for ink jet-imprintable constructions |
AU39696/99A AU3969699A (en) | 1998-05-01 | 1999-05-03 | Water-activatable polymers for ink jet-imprintable constructions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/701,767 US5969069A (en) | 1995-08-25 | 1996-08-26 | Water-activatable polymers and printable constructions |
US09/071,502 | 1998-05-01 |
Publications (1)
Publication Number | Publication Date |
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WO1999057215A1 true WO1999057215A1 (en) | 1999-11-11 |
Family
ID=24818590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/009682 WO1999057215A1 (en) | 1996-08-26 | 1999-05-03 | Water-activatable polymers for ink jet-imprintable constructions |
Country Status (2)
Country | Link |
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US (1) | US5969069A (en) |
WO (1) | WO1999057215A1 (en) |
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EP1106372A3 (en) * | 1999-11-29 | 2001-08-16 | Seiko Epson Corporation | Recording medium, manufacturing method thereof and recording method and recorded matter using the same |
JP2002086996A (en) * | 2000-09-18 | 2002-03-26 | Goo Chemical Co Ltd | Ink jet transfer medium as well as transfer material using the same, method for transferring and transfer product |
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EP1106372A3 (en) * | 1999-11-29 | 2001-08-16 | Seiko Epson Corporation | Recording medium, manufacturing method thereof and recording method and recorded matter using the same |
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JP2002086996A (en) * | 2000-09-18 | 2002-03-26 | Goo Chemical Co Ltd | Ink jet transfer medium as well as transfer material using the same, method for transferring and transfer product |
JP4502236B2 (en) * | 2000-09-18 | 2010-07-14 | 互応化学工業株式会社 | Transfer method and transfer product using transfer material obtained from transfer medium for inkjet |
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WO2009113097A3 (en) * | 2008-01-31 | 2013-02-28 | Bilcare Limited | Process for printing a plastic film with water containing inks and water containing additives |
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